Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

Abstract

We consider several spin-unrestricted random-phase approximation (RPA) variants for calculating correlation energies, with and without range separation, and test them on datasets of atomization energies and reaction barrier heights. We show that range separation greatly improves the accuracy of all RPA variants for these properties. Moreover, we show that a RPA variant with exchange, hereafter referred to as RPAx-SO2, first proposed by Sz-abo and Ostlund [A. Szabo and N. S. Ostlund, J. Chem. Phys. 67, 4351 (1977)] in a spin-restricted closed-shell formalism, and extended here to a spin-unrestricted formalism , provides on average the most accurate range-separated RPA variant for atomization energies and reaction barrier heights. Since this range-separated RPAx-SO2 method had already been shown to be among the most accurate range-separated RPA variants for weak intermolecular interactions [J. Toulouse, W. Zhu, A. Savin, G. Jansen, and J. G. {Á}ngy{á}n, J. Chem. Phys. 135, 084119 (2011)], this works confirms range-separated RPAx-SO2 as a promising method for general chemical applications.

References in corpus (11)

• The Ground State Correlation Energy of the Random Phase Approximation from a Ring Coupled Cluster Doubles Approach
• Adiabatic-connection fluctuation-dissipation density-functional theory based on range separation
• Long-range-corrected hybrids including RPA correlation
• Efficient and accurate calculation of exact exchange and RPA correlation energies in the Adiabatic-Connection Fluctuation-Dissipation theory
• Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions
• Correlation energy expressions from the adiabatic-connection fluctuation-dissipation theorem approach
• Range-separated density-functional theory with random phase approximation: detailed formalism and illustrative applications
• Basis convergence of range-separated density-functional theory
• Short range DFT combined with long-range local RPA within a range-separated hybrid DFT framework
• Analytical Energy Gradients in Range-Separated Hybrid Density Functional Theory with Random Phase Approximation
• Accuracy of basis-set extrapolation schemes for DFT-RPA correlation energies in molecular calculations

Cited by in corpus (11)

• A general range-separated double-hybrid density-functional theory
• A Density-Based Basis-Set Correction For Wave Function Theory
• Chemically Accurate Excitation Energies With Small Basis Sets
• A basis-set error correction based on density-functional theory for strongly correlated molecular systems
• Fractional-charge and fractional-spin errors in range-separated density-functional theory
• Range-separated double-hybrid density-functional theory with coupled-cluster and random-phase approximations
• Self-consistent range-separated density-functional theory with second-order perturbative correction via the optimized-effective-potential method
• A new form of transcorrelated Hamiltonian inspired by range-separated DFT
• Restoring the Pauli principle in the random phase approximation ground state
• Expectation values of single-particle operators in the random phase approximation ground state
• Random Phase Approximation in Projected Oscillator Orbitals